Method for producing a group iii nitride semiconductor

ABSTRACT

A method for producing a Group III nitride semiconductor includes feeding a nitrogen-containing gas into a molten mixture of a Group III metal and a flux placed in a furnace, to thereby grow a Group III nitride semiconductor on a seed substrate, wherein the Group III nitride semiconductor is grown on the seed substrate, while controlling the surface modification weight ratio, which is defined as the ratio of the weight of Na including a portion surface-modified through oxidation or hydroxidation to the weight of Na when the surface thereof has no surface-modified portion as a reference weight, with Na serving as the flux.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a Divisional Application of U.S. patentapplication Ser. No. 17/531,982, filed on Nov. 22, 2021, which is aDivisional Application of Ser. No. 16/814,758, filed on Mar. 10, 2020,now U.S. Pat. No. 11,280,024, which is based on Japanese PatentApplication No. 2019-050287, filed on Mar. 18, 2019, Japanese PatentApplication No. 2019-069498, filed on Mar. 30, 2019, and Japanese PatentApplication No 2019-069511, filed on Mar. 30, 2019, the contents ofwhich are incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a method for producing a Group IIInitride semiconductor through a flux method.

Background Art

A flux method is a known technique for the crystal growth of a Group IIInitride semiconductor, in which nitrogen is dissolved in a moltenmixture of an alkali metal and a Group III element (e.g., Ga), tothereby achieve epitaxial growth of a Group III nitride semiconductor inthe liquid phase. Generally, sodium (Na) is used as the alkali metal.When Na is used as a flux, the technique is called an Na flux method.

Japanese Patent Application Laid-Open (kokai) No. 2016-160151 disclosesthat oxygen is readily incorporated into a Group III nitridesemiconductor crystal which is grown through an Na flux method.Particularly in the case of the 3-dimensional growth mode, oxygen intakeincreases.

In the production of a Group III nitride semiconductor crystal through aflux method disclosed in Japanese Patent Application Laid-Open (kokai)No. 2016-160151, the oxygen atom concentration in the vicinity of a mainface of the crystal is controlled to 1×10¹⁷/cm³ or less. As a result,even in the case where a thick layer of a Group III nitridesemiconductor crystal is formed through, for example, hydride vaporphase epitaxy (HVPE) on a Group III nitride semiconductor crystal whichhas been grown through a flux method, warpage and cracks of a substrate,which would otherwise be caused by lattice distortion due to oxygenatoms, can be suppressed.

An example of a seed substrate is a template substrate composed of asapphire substrate or the like and a gallium nitride layer (GaN layer)grown on the substrate through metalorganic chemical vapor deposition(MOCVD). In a specific procedure, a seed substrate, a Group III metal(e.g., Ga), and Na are placed in a crucible, and the crucible is heatedin a reaction chamber. Pressurized nitrogen is fed into the chamber, tothereby yield a melt containing Ga and Na. Then, while the temperatureand pressure in the chamber are controlled, a single crystal of a GroupIII nitride semiconductor (e.g., GaN) is grown on a seed substrateplaced in the melt.

As disclosed in Japanese Patent Application Laid-Open (kokai) No.2008-254999, the purity of sodium employed in the flux method must beenhanced. For preventing oxidation of the surface of Na liquid, an Napurifying apparatus and a glovebox, both being isolated from atmosphere,are employed. Also, a surface oxide layer of Na is scraped off.

In crystal growth of a Group III nitride semiconductor through the fluxmethod, occurrence of anomalous growth at the periphery of the seedsubstrate is problematic. The concept “anomalous growth” refers tofailure to achieve crystal growth of a Group III nitride semiconductoron the seed substrate and growth of anomalous grains (i.e., crystalgrains greater in size than normally grown grains).

Another problem is occurrence of warpage in the seed substrate, and thedegree of warpage tends to vary between product lots. Such warpage iscaused by slight lattice mismatch between the template substrate (a GaNcrystal) grown through vapor phase growth and the GaN crystal grownthrough the flux method. In the flux method, oxygen attributed tooxidized sodium is readily incorporated into crystals during growth, andthe amount of oxygen incorporation varies depending on the mode ofgrowth. The oxygen profile in the grown crystal determines generation oflattice mismatch.

Thus, when the seed substrate has warpage, fracture and cracks of thegrown GaN single crystal occur, and the crystallinity thereof isimpaired. Both cases are problematic. In the case where a grownsemiconductor single crystal having warpage is used as a substrate foranother use, the surface of the substrate is flattened though polishing.However, the angle (off angle) formed by the normal of the polishedsurface of the substrate and the crystal growth axis (e.g., c axis)varies on the substrate surface, thereby failing to ensure uniformity.As a result, the crystal orientation along the normal of any of thesemiconductor layers of a device grown on the substrate fails to haveuniformity. This leads to lack of uniformity in device characteristicsobtained from a single wafer. Therefore, occurrence of warpage of asemiconductor single crystal grown through a flux method must besuppressed.

Also, when sodium is slightly oxidized or contains a large amount ofimpurities, miscellaneous crystals tend to generate in a crucible forwhich a semiconductor single crystal is grown. Such miscellaneouscrystals adversely affect the growth of a semiconductor single crystal,impair the crystallinity of the semiconductor single crystal, and reducethe yield of the semiconductor single crystal.

SUMMARY OF THE INVENTION

The present invention has been conceived to solve the problems involvedin the aforementioned conventional techniques. Thus, an object of thepresent invention is to suppress anomalous growth of a Group III nitridesemiconductor at the periphery of a seed substrate.

Another object of the invention is to suppress at least one ofoccurrence of warpage of a Group III nitride semiconductor singlecrystal and generation of miscellaneous crystals.

Yet another object of the invention is to suppress at least one ofoccurrence of warpage of a Group III nitride semiconductor singlecrystal and generation of miscellaneous crystals, through controllingthe amount of oxygen incorporated into an Na material.

These objects are to be attained by a relevant aspect of the presentinvention, and no single aspect necessarily attains all the objects.

In view of the foregoing, the present inventors have carried outextensive studies, and have found that anomalous growth at the peripheryof the seed substrate can be suppressed by controlling the oxygenconcentration of an atmosphere for the growth of a Group III nitridesemiconductor during the growth. A first aspect of the present inventionhas been accomplished on the basis of this finding.

According to a technical feature of the first aspect of the presentinvention, in the Group III nitride semiconductor production methodwhich includes feeding a nitrogen-containing gas into a molten mixtureof a Group III metal and a flux placed in a furnace, to thereby grow aGroup III nitride semiconductor on a seed substrate, the oxygenconcentration of the atmosphere inside the furnace (hereinafter may bereferred to as “furnace internal atmosphere”) is elevated after thegrowth initiation temperature of the Group III nitride semiconductor hasbeen achieved.

In the first aspect of the present invention, the following mode may beemployed. The elevation of the oxygen concentration may be in a gradualmanner or a stepwise manner at the growth initiation temperature orhigher. Preferably, the oxygen concentration of the furnace internalatmosphere before achieving the growth initiation temperature iscontrolled to 0.02 ppm or less and greater than 0 ppm. In the periodfrom the initiation of the growth of the Group III nitride semiconductorto a certain timing, desirably, the oxygen concentration of the furnaceinternal atmosphere is controlled to 0.02 ppm or less and greater than 0ppm, and thereafter, to greater than 0.02 ppm and 0.1 ppm or less. Theabove period is preferably adjusted to 5 to 15 hours after theinitiation of the growth of the Group III nitride semiconductor. Whenthe period falls within the above range, anomalous growth at theperiphery of the seed substrate can be more effectively suppressed.Also, the oxygen concentration of the furnace internal atmosphere may becontrolled by means of the oxygen concentration of thenitrogen-containing gas which is fed to the molten mixture. Further, theoxygen concentration of the furnace internal atmosphere may be regulatedby means of the oxygen concentration of the atmosphere outside thefurnace (hereinafter may be referred to as “furnace externalatmosphere”).

In the above description, the term “oxygen concentration” is on a volumebasis. Also, the timing of initiating the growth of the Group IIInitride semiconductor refers to that the timing at which the growthtemperature and pressure are achieved through heating and pressurizing.The term “furnace internal atmosphere” refers to the atmosphere of thechamber of the furnace in which the molten mixture is placed; morespecifically to the gas which is in contact with the molten mixture. Theoxygen concentration of the furnace internal atmosphere is controlledthrough, for example, the following procedures. In one procedure, theoxygen concentration of the furnace internal atmosphere is regulated bythe oxygen concentration of the nitrogen-containing gas fed to themolten mixture, whereby the oxygen concentration of the furnace internalatmosphere can be directly controlled. In another procedure, the oxygenconcentration of the furnace internal atmosphere is regulated by that ofthe furnace external atmosphere. In the case where the inside and theoutside of the furnace are not definitely isolated from each other dueto the structural feature of the crystal growth apparatus, the furnaceexternal atmosphere may have slight impact on the furnace internalatmosphere. However, through employment of the effect, the oxygenconcentration of the furnace internal atmosphere may be indirectlycontrolled. At this time, the furnace is preferably preheated (baked)before the growth to prevent gas from being generated from the furnace.The oxygen concentration of the furnace internal atmosphere may also becontrolled by preheating.

A second aspect of the present invention is directed to a Group IIInitride semiconductor production method which includes feeding anitrogen-containing gas into a molten mixture of a Group III metal and aflux placed in a furnace, to thereby grow a Group III nitridesemiconductor on a seed substrate. A technical feature of the secondaspect resides in the Group III nitride semiconductor being grown on theseed substrate, while controlling the surface modification weight ratio,which is defined as the ratio of the weight of Na including a portionsurface-modified through oxidation or hydroxidation to the weight of Nawhen the surface thereof has no surface-modified portion as a referenceweight, with Na serving as the flux.

In the second aspect of the present invention, the following mode may beemployed. The surface modification weight ratio (=(referenceweight+weight increase by surface modification)/reference weight) ispreferably controlled to 1.000002 to 1.001. That is, the ratio of weightincrease by surface modification to reference weight (=weight increaseby surface modification/reference weight) is preferably controlled to2×10⁻⁶ to 1×10⁻³. The surface modification weight ratio may be adjustedto 1.00002 to 1.0001. That is, the ratio of weight increase by surfacemodification to reference weight is preferably adjusted to 2×10⁻⁵ to1×10⁻⁴. When the above conditions are satisfied, generation ofmiscellaneous crystals can be effectively suppressed. The surfacemodification weight ratio may be adjusted to 1.000002 to 1.00005. Thatis, the ratio of weight increase by surface modification to referenceweight is preferably adjusted to 2×10⁻⁶ to 5×10⁻⁵. When the condition issatisfied, warpage of the substrate after growth of the target crystalcan be effectively prevented.

Alternatively, the surface modification weight ratio may be modified bymaintaining Na in a specific environment outside the furnace before itsentrance to the furnace. In one possible procedure, Na is maintained fora predetermined period in a sealed container where the oxygenconcentration and water content are controlled. In this case, Na absorbsoxygen and water (referring to inclusion of water vapor, in thespecification) present in the sealed container to equilibrium, wherebythe oxygen concentration and water content of Na attain constant values.Still alternatively, the surface modification weight ratio may bemodified by feeding a gas mixture containing at least one of oxygen andwater to the furnace. In this case, the oxygen concentration and watercontent of the specific environment are preferably controlled to ≤0.05ppm and >0 ppm, respectively. Also, to the specific environment, a gasmixture containing at least one of oxygen and water may be introduced.In a preferred procedure, an Na piece whose surface modification weightratio has been controlled is cut, and a carbon material is placed on asurface of the cut piece which has undergone no oxidation orhydroxidation, followed by placing the resultant piece in the furnace.Through this process, carbon can be dispersed in molten Na in a moreuniform manner.

According to the Group III nitride semiconductor single crystalproduction method of the second aspect of the present invention,occurrence of warpage of the Group III nitride semiconductor singlecrystal can be suppressed. Also, the amount of miscellaneous crystalsgenerated can be suppressed. Moreover, reproducibility in quality of thesemiconductor single crystal between production batches and productionyield are improved.

A third aspect of the present invention is directed to a Group IIInitride semiconductor production method which includes feeding anitrogen-containing gas into a molten mixture of a Group III metal and aflux placed in a furnace, to thereby grow a Group III nitridesemiconductor on a seed substrate. A technical feature of the thirdaspect resides in that at least the oxidation amount of Na serving asthe flux is controlled outside the furnace, and the thus-controlled Nais fed into the furnace.

In the third aspect of the present invention, the following mode may beemployed. Specifically, molten Na prepared by liquefying Na iscirculated through a first state where the temperature is maintained ata first temperature and a second state where the temperature ismaintained at a second temperature lower than the first temperature, tothereby remove oxidized Na contained in the molten Na in the secondstate. The oxidation amount may be regulated by modifying the secondtemperature. In the third aspect, the second temperature is preferablycontrolled to 120° C. to 300° C. Circulation of molten Na performed forcontrolling the oxidation amount and the purity of Na is conducted bymeans of a circulation apparatus. In one embodiment, the Na circulationapparatus includes a circulation path for converting the Na material toliquid and causing the liquid to flow, and the circulation path includesan Na purity control section maintained at the second temperature and apipe. In the apparatus of this configuration, the Na circulation pathmay include an Na-storing section, and the temperatures of theNa-storing section and the pipe may be adjusted to be higher than thatof the Na purity control section.

According to the first aspect of the present invention, anomalouscrystal growth at the periphery of the seed substrate can be suppressed,whereby a uniform and flat Group III nitride semiconductor layer can begrown on the seed substrate. According to the second and third aspectsof the present invention, at least one of occurrence of warpage of theGroup III nitride semiconductor single crystal and generation ofmiscellaneous crystals can be suppressed.

BRIEF DESCRIPTION OF DRAWINGS

Various other objects, features, and many of the attendant advantages ofthe present invention will be readily appreciated as the same becomesbetter understood with reference to the following detailed descriptionof the preferred embodiments when considered in connection with theaccompanying drawings, in which:

FIG. 1 is a sketch showing the configuration of a crystal growthapparatus according to one embodiment of the present invention;

FIG. 2 is a flow chart showing growth steps of the Group III nitridesemiconductor of the first embodiment;

FIG. 3 is a graph showing the relationship between oxygen concentrationand growth time in the first embodiment;

FIGS. 4A-4B are photographs of a seed substrate taken after growth ofGaN crystal according to Example 1;

FIGS. 5A-5B are photographs of a seed substrate taken after growth ofGaN crystal according to Comparative Example 1;

FIGS. 6A-6B are photographs of a seed substrate taken after growth ofGaN crystal according to Comparative Example 2;

FIG. 7 is a sketch showing the stack structure of a semiconductorproduced through an embodiment of the present invention;

FIG. 8 is a conceptual and general representation of a productionapparatus employed in a production method according an embodiment;

FIG. 9 is a schematic configuration of an Na circulation apparatus;

FIG. 10 is a schematic configuration of a glovebox for producing asemiconductor single crystal;

FIG. 11 is a sketch of large grains grown on a seed substrate at aninitial stage of semiconductor growth;

FIG. 12 is a sketch of small grains grown on a seed substrate at aninitial stage of semiconductor growth;

FIG. 13 is a sketch showing the definition of the size of a grain grownon a seed substrate at an initial stage of semiconductor growth;

FIG. 14 is a sketch of a seed substrate;

FIG. 15 a sketch of a jig employed in a semiconductor single crystalproduction method of an embodiment;

FIG. 16 is a sketch showing modification of the surface of asemiconductor according to a production method of an embodiment;

FIG. 17 is a sketch showing the contact between carbon and anon-oxidized surface of Na in a crucible according to a productionmethod of an embodiment;

FIG. 18 is a sketch showing the contact between carbon and an oxidizedsurface of Na in a crucible according to a production method of anembodiment;

FIG. 19 is a graph showing the relationship between Na surfacemodification weight ratio and warpage (curvature) or amount ofmiscellaneous crystals in a production method according to a secondembodiment;

FIG. 20 is a graph showing the relationship between cold traptemperature and warpage (curvature) or amount of miscellaneous crystalsin a production method according to a third embodiment;

FIG. 21A is a cross-section of another example of the seed substrate;

FIG. 21B is a plan view of the example of the seed substrate.

FIG. 22A is a cross-section of another example of the seed substrate;

FIG. 22B is a cross-section of a semiconductor grown on the seedsubstrate;

FIG. 22C is a cross-section of another example of the seed substratefollowing FIG. 22B; and

FIG. 22D is a cross-section of another example of the seed substratefollowing FIG. 22C.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Specific embodiments of the present invention are directed to growth ofa Group III nitride semiconductor crystal on a seed substrate through aflux method. First, the flux method will be described generally.

1. General Description of Flux Method

The flux method employed in the embodiments of the invention is atechnique which includes feeding a nitrogen-containing gas to a moltenmixture containing an alkali metal (flux) and a Group III metal (rawmaterial), and dissolving the gas in the molten mixture, to therebyachieve epitaxial growth of a Group III nitride semiconductor in aliquid phase.

The Group III metal, serving as a raw material, is at least one metalselected from among gallium (Ga), aluminum (Al), and indium (In).Through modifying the proportions of the metal elements, the compositionof the formed Group III nitride semiconductor can be controlled, andspecifically, GaN, AlN, InN, AlGaN, InGaN, AlGaInN, and othersemiconductors can be grown. Use of only Ga as a Group III metal isparticularly preferred. In other words, the present invention isparticularly suitable for the growth of GaN. The alkali metal serving asa flux is generally sodium (Na), but potassium (K) or a mixture of Naand K may also be used. Furthermore, lithium (Li) or an alkaline earthmetal may also be added.

To the molten mixture, carbon (C) may also be added. Addition of carbonresults in acceleration of crystal growth. A dopant other than C mayalso be added to the molten mixture, for the purpose of controllingphysical properties (e.g., the type conduction and magnetic properties)of the grown Group III nitride semiconductor, promoting crystal growth,suppressing generation of miscellaneous crystals, regulating the growthdirection, or the like. For example, germanium (Ge) or the like may beused as an n-type dopant, and magnesium (Mg), zinc (Zn), calcium (Ca),or the like may be used as a p-type dopant. The nitrogen-containing gasis a gas of nitrogen molecules, a gas of a compound including a nitrogenelement (e.g., ammonia), or a mixture thereof. The nitrogen-containinggas may be mixed with an inert gas such as a rare gas.

2. Structure of Seed Substrate

In the embodiments, a seed substrate (seed crystal) is placed in themolten mixture, and a Group III nitride semiconductor is grown on theseed substrate. The seed substrate may be placed in the molten mixturebefore heating or pressurization or after achieving growth temperatureand pressure through heating and pressurization. As the seed substrate,a self-standing substrate or a template substrate made of a Group IIInitride semiconductor may be used. The self-standing substrate may beformed of a Group III nitride semiconductor having arbitrarycompositional proportions such as GaN, AlGaN, or AlN. Generally, a GroupIII nitride semiconductor having the same composition as that of theGroup III nitride semiconductor to be grown through the flux method isused.

The template substrate is formed of an underlayer substrate, a bufferlayer provided on the underlayer substrate, and a Group III nitridesemiconductor layer which has a c-plane as a main plane and which isprovided on the buffer layer. For example, the template substrate has astructure shown in FIG. 14 . Also, as shown in FIGS. 21A and 21B, theremay be used a substrate formed of an underlayer substrate on which aplurality of Group III nitride semiconductor columns (e.g., roundcolumn, hexagonal prism, hexagonal pyramid, truncated hexagonal pyramid,etc.) pieces are arranged. The underlayer substrate may be formed of anymaterial, so long that it allows a Group III nitride semiconductor to begrown on the substrate. Examples of the material which may be used inthe invention include sapphire, ZnO, and spinel. The Group III nitridesemiconductor layer provided on the underlayer substrate may be formedof a Group III nitride semiconductor having arbitrary compositionalproportions such as GaN, AlGaN, or AlN. Generally, a Group III nitridesemiconductor having the same composition as that of the Group IIInitride semiconductor to be grown through the flux method is used. TheGroup III nitride semiconductor layer may be formed through anytechnique such as MOCVD, HVPE, or MBE. However, from the viewpoints ofcrystallinity and growth time, MOCVD and HVPE are preferred.

3. Configuration of Crystal Growth Apparatus

In the Group III nitride semiconductor production method according to anembodiment of the present invention, a crystal growth apparatus 1000having, for example, the following configuration is employed.

FIG. 1 is a sketch showing the configuration of the crystal growthapparatus 1000. The crystal growth apparatus 1000 is employed for thegrowth of a Group III nitride semiconductor single crystal on a growthsubstrate through an Na flux method. As shown in FIG. 1 , the crystalgrowth apparatus 1000 has a pressure vessel 1100, a pressure vessel lid1110, a middle chamber 1200, a reaction chamber 1300, a reaction chamberlid 1310, a rotation axis 1320, a turn table 1330, a side heater 1410, alower heater 1420, a gas intake inlet 1510, a gas exhaust outlet 1520, avacuum exhaust outlet 1530, a measurement ventilation hole 1540, and aQmass mounting port 1550.

The pressure vessel 1100 serves as a housing of the crystal growthapparatus 1000. The pressure vessel lid 1110 is disposed under thepressure vessel 1100 in an orthogonal direction. The middle chamber 1200is a chamber disposed inside the pressure vessel 1100. The reactionchamber 1300 is a chamber for accommodating a crucible CB1, in which asemiconductor single crystal is to be grown. The reaction chamber lid1310 serves as a lid for the reaction chamber 1300. The rotation axis1320 is adapted to regular rotation and reverse rotation. The rotationaxis 1320 receives rotary drive by a motor (not illustrated). The turntable 1330 allows rotation following the rotation axis 1320. The sideheater 1410 and the lower heater 1420 are provided for heating thereaction chamber 1300.

The gas intake inlet 1510 is an inlet through which anitrogen-containing gas is fed into the pressure vessel 1100. The gasexhaust outlet 1520 is an outlet through which a gas inside the pressurevessel 1100 is discharged. The vacuum exhaust outlet 1530 is an outletfor evacuating the pressure vessel 1100. The measurement ventilationhole 1540 is a hole through which a gas inside the pressure vessel 1100is extracted for assay. On the gas flow downstream side of theventilation hole 1540, an O₂ sensor and a dew point meter are disposed.The Qmass mounting port 1550 is disposed for mounting a Qmass apparatus.The crystal growth apparatus 1000 enables regulation of the temperatureand pressure inside the crucible CB1 and rotating the crucible CB1.Thus, in the crucible CB1, a semiconductor single crystal can be grownfrom a seed crystal under conditions of interest.

First Embodiment

A first embodiment is directed to a method for controlling the oxygenconcentration of the furnace internal atmosphere.

In the crystal growth apparatus 1000, the oxygen concentration of thefurnace internal atmosphere (i.e., the atmosphere inside the reactionchamber 1300) is controlled by regulating the oxygen concentration ofthe nitrogen-containing gas fed into the reaction chamber 1300 throughthe gas intake inlet 1510. In the case where the furnace internalatmosphere and the furnace external atmosphere (the atmosphere outsidethe pressure vessel 1100) are not definitely isolated from each otherdue to the structural feature of the crystal growth apparatus 1000, thefurnace external atmosphere may have slight impact on the furnaceinternal atmosphere. On the basis of the phenomenon, the oxygenconcentration of the furnace internal atmosphere may be controlled bycontrolling the oxygen concentration of the furnace external atmosphere.In this case, desirably, an additional chamber (i.e., a lower chamber)which embraces the gap between the pressure vessel 1100 and the pressurevessel lid 1110 is provided, and the oxygen concentration of theatmosphere of the additional chamber is controlled.

1. Group III Nitride Semiconductor Production Method

Next, the Group III nitride semiconductor production method according tothe first embodiment will be described, with reference to relevantdrawings. Firstly, the furnace internal atmosphere is substituted byinert gas, and the furnace is heated. Thereafter, the furnace isevacuated so as to satisfactorily reduce the out gas component (e.g.,oxygen) level. Then, the alkali metal and Group III metal are weighed ina glovebox in which the atmosphere (e.g., oxygen and dew point) iscontrolled. Subsequently, the seed substrate and the thus-weighed alkalimetal and the Group III metal in specific amounts are added to thecrucible CB1. If needed, an additional element such as carbon may befurther added.

Then, the crucible CB1 to which the raw materials have been added isplaced on the turn table 1330 of the reaction chamber 1300, and thereaction chamber 1300 is closed. Further, the reaction chamber 1300 isconfined in the pressure vessel 1100. Thereafter, the reaction chamber1300 and the pressure vessel 1100 are evacuated, and anitrogen-containing gas is fed into the reaction chamber 1300 and thepressure vessel 1100. When the pressure reached the crystal growthlevel, the inside temperature of the furnace is elevated to the crystalgrowth temperature. For example, the crystal growth temperature is 700°C. to 1,000° C., and the crystal growth pressure is 2 MPa to 10 MPa. Inthe course of temperature elevation, the alkali metal and the Group IIImetal in solid form are melted in the crucible CB1, to thereby form aliquid molten mixture.

When the temperature inside the reaction chamber 1300 has reached thecrystal growth temperature, the crucible CB1 is preferably rotated.Whereby the molten mixture is stirred, to thereby achieve a uniformmixing state of the molten mixture where the alkali metal concentrationand the Group III metal concentration become uniform. When nitrogen isgradually dissolved in the molten mixture to a supersaturated state,growth of a Group III nitride semiconductor on the upper surface of theseed substrate begins. Notably, stirring may be initiated beforeachieving the crystal growth temperature in the reaction chamber 1300.While the crystal growth temperature and pressure are maintained, aGroup III nitride semiconductor crystal is sufficiently grown on theupper surface of the seed substrate 1. Then, the rotation of thecrucible CB1 and heating of the reaction chamber 1300 are terminated,whereby the temperature is lowered to room temperature, and the pressureis reduced to normal pressure. At this timing, growth of the Group IIInitride semiconductor is terminated.

In the Group III nitride semiconductor production method of the firstembodiment, the growth is initiated at the timing where the crystalgrowth temperature and pressure have been achieved. During the coursefrom the timing of growth initiation to a specific time, the oxygenconcentration of the furnace internal atmosphere is controlled to be0.02 ppm or less (first step, step S1 in FIG. 2 ). Herein, the term“oxygen concentration” is defined as a volume basis concentration. Theconcept “furnace internal atmosphere” refers to the atmosphere of thereaction chamber 1300 in which the molten mixture is placed, morespecifically to the gas which is in contact with the molten mixture. Inorder to reduce the oxygen concentration of the furnace internalatmosphere to 0.02 ppm or less, the oxygen concentration of the furnaceexternal atmosphere is preferably reduced to as low a level as possible.In the case where the furnace internal atmosphere and the furnaceexternal atmosphere (the atmosphere outside the pressure vessel 1100)are not definitely isolated from each other due to the structuralfeatures of the crystal growth apparatus 1000, oxygen enters the furnacethrough, for example, the space at the opening/closing port of thefurnace, whereby the furnace external atmosphere may have slight impacton the oxygen concentration of the furnace internal atmosphere. When alower chamber is disposed under the crystal growth apparatus 1000, theatmosphere of the lower chamber is preferably substituted by an inertgas such as nitrogen.

In the first Group III nitride semiconductor growth step, the growthtime is preferably set to 5 to 15 hours. Under the conditions, anomalousgrowth at the periphery of the seed substrate can be more effectivelysuppressed. The growth time is more preferably 7 to 13 hours, still morepreferably 9 to 11 hours. In the first step, the oxygen concentration ofthe furnace internal atmosphere is not necessarily constant, so long asit is 0.02 ppm or lower. More specifically, the oxygen concentration maybe elevated in a continuous or stepwise manner. Notably, a morepreferred oxygen concentration of the furnace internal atmosphere in thefirst step is 0.015 ppm or lower, more preferably 0.01 ppm or lower.Although the oxygen concentration is desirably lower, it is preferably0.005 ppm or higher, from the viewpoints of ease of control and cost.

Subsequently, after the first step (i.e., from the initiation of thegrowth of the Group III nitride semiconductor to elapse of a certaintime), the oxygen concentration of the furnace internal atmosphere iscontrolled to >0.02 ppm and to 0.1 ppm or lower (second step, step S2 inFIG. 2 ). In the second step, the oxygen concentration of the furnaceinternal atmosphere is not necessarily constant, so long as it is >0.02ppm and 0.1 ppm or lower. More specifically, the oxygen concentrationmay be elevated in a continuous or stepwise manner. Alternatively, theoxygen concentration is not necessarily changed in a stepwise mannerfrom the first step to the second step, and it may be continuouslychanged.

As described above, in the first embodiment, the oxygen concentration ofthe furnace internal atmosphere during the period of initiation of thegrowth to a specific time is controlled to 0.02 ppm or lower. Then, theoxygen concentration of the furnace internal atmosphere is controlled tobe >0.02 ppm and 0.1 ppm or lower. Through controlling the oxygenconcentration in the above manner, anomalous growth at the periphery ofthe seed substrate can be suppressed, whereby a flat and uniform GroupIII nitride semiconductor crystal layer can be formed on the seedsubstrate.

No precise mechanism has been elucidated for suppressing anomalousgrowth at the periphery of the seed substrate through controlling theoxygen concentration of the furnace internal atmosphere. However, aconceivable mechanism is as follows. In an initial stage of crystalgrowth, the following reaction is thought to occur in accordance withthe oxygen content of the molten mixture.

In the initial stage of crystal growth, when the molten mixture has alower oxygen content, conceivably, nitrogen which is present in thecrucible CB1 in the vicinity of the side wall and which is dissolved inthe molten mixture is consumed due to a certain reaction. As a result, aportion of the molten mixture in the vicinity of the side wall ofcrucible CB1 attains a nitrogen-unsaturated state, and the peripheralportion of the seed substrate undergoes melting back, to thereby causeanomalous growth. In the initial stage of crystal growth, when themolten mixture has an appropriate oxygen concentration, theaforementioned reaction in the vicinity of the side wall of crucible CB1is thought to be suppressed. Thus, even in the vicinity of the side wallof crucible CB1, a large amount of nitrogen is dissolved. In this case,nitrogen is supersaturated in the molten mixture, to thereby preventmelting back at the periphery of the seed substrate. In the initialstage of crystal growth, when the molten mixture contains an excessamount of oxygen, the surface of the molten mixture is covered withoxide film. The formation of the oxide film is conceivably morelocalized at the side wall of the crucible CB1 when the crucible CB1 isrotated, as the crucible CB1 rotates. By virtue of the oxide film, theamount of nitrogen dissolved in the molten mixture decreases, andnitrogen is unsaturated in the molten mixture. As a result, melting backoccurs at the periphery of the seed substrate, leading to anomalousgrowth.

According to the first embodiment in which the oxygen concentration iscontrolled, the oxygen content of the molten mixture in the initialstage of crystal growth is adjusted to a moderate level. As a result,conceivably, melting back at the periphery of the seed substrate issuppressed, and anomalous growth is suppressed.

2. Method for Controlling Oxygen Concentration

One method for controlling the oxygen concentration of the furnaceinternal atmosphere is to manage the furnace in which the furnace isplaced (i.e., furnace external atmosphere). In some structures of thecrystal growth apparatus 1000, isolation between the furnace internalatmosphere and the furnace external atmosphere is not completelyachieved. In such a case, when the oxygen concentration of the furnaceexternal atmosphere varies, the amount of oxygen migrating into thespace of the furnace also varies. Thus, the oxygen concentration of thefurnace internal atmosphere varies. On the basis of the phenomenon, theoxygen concentration of the furnace internal atmosphere may becontrolled by the oxygen concentration of the furnace externalatmosphere.

Another method for controlling the oxygen concentration is modifying theoxygen concentration of the nitrogen-containing gas fed to the furnace(i.e., the gas fed to the reaction chamber 1300). Through thistechnique, the oxygen concentration of the furnace internal atmospherecan be directly controlled. The oxygen concentration of the gas fedthrough the gas intake inlet 1510 to the reaction chamber 1300 may beregulated. Alternatively, an additional oxygen intake inlet is attachedto the reaction chamber 1300, and the oxygen concentration of the gasflowing through the inlet to the reaction chamber 1300 may be regulated.

With reference to the drawings, the first embodiment will next bedescribed in detail by way of working examples, which should not beconstrued as limiting the present invention thereto.

Example 1

By use of the crystal growth apparatus 1000, a GaN crystal was grown ona seed substrate in the following manner. Firstly, the atmosphere of thefurnace (reaction chamber 1300 and pressure vessel 1100) was substitutedby nitrogen gas. The furnace was heated and evacuated, to thereby reducethe amounts of oxygen and water. Through this process, the oxygenconcentration of the furnace internal atmosphere was adjusted to 0.02ppm or lower at the start of growth of a GaN crystal. Subsequently, acrucible CB1 made of alumina was placed in a glovebox, and a seedcrystal, Ga (solid), and Na (solid) were placed in the crucible. Inorder to enhance the growth rate, graphite powder was added to thecrucible CB1. A seed substrate formed of a sapphire substrate on which aflat and uniform GaN layer had been provided through MOCVD was used.

Then, the crucible CB1 was transferred to a furnace, and the furnace wastightly closed. Nitrogen was fed to the furnace so as to adjust theinternal pressure to 3 MPa. For preventing oxidation of Na in thecrucible CB1 in the glovebox and the transfer path, the atmosphere ofthe lower chamber was controlled, and the crucible CB1 was put in aspecific container for its transfer to the furnace. Thereafter, thefurnace was heated to the growth temperature (856° C.), whereby growthof a GaN crystal on the seed substrate was started. When the temperaturereached the growth temperature, the nitrogen atmosphere of the lowerchamber sealing the opening/closing port of the pressure vessel 1100 wassubstituted by dry air. Thus, air gradually entered from the outside ofthe furnace to the pressure vessel 1100, and further from the pressurevessel 1100 to the reaction chamber 1300.

FIG. 3 is a graph showing the relationship between the growth time (timeafter achieving to growth temperature) and the oxygen concentration ofthe furnace internal atmosphere. The oxygen concentration of the gasdischarged from the reaction chamber 1300 through the gas exhaust outlet1520 was measured, and the obtained measurement was employed as theoxygen concentration of the furnace internal atmosphere. As shown inFIG. 3 , the oxygen concentration of the furnace internal atmosphere was0.015 ppm at the start of growth, and gradually increased with the lapseof time. Ten hours after the start of growth, the oxygen concentrationreached 0.02 ppm. Thereafter, the oxygen concentration continuouslyincreased, and was about 0.07 ppm after 40 hours.

Forty hours after the start of growth of a GaN crystal, the temperatureand pressure were changed to ambient temperature and normal pressure,whereby the growth of a GaN crystal was terminated. The seed substratewas removed from the furnace and washed with ethanol or the like, tothereby remove Na and Ga. FIG. 4A is a photograph of a surface of theseed substrate (GaN crystal growth side), and FIG. 4B is a fluorescentimage of the surface of the seed substrate. Observation of the GaNcrystal formed on the seed substrate shows that GaN was uniformly grownon the entire surface of the seed substrate. The average film thicknesswas found to be 0.5 mm, and no anomalous growth was observed at theperiphery of the seed substrate.

Comparative Example 1

The procedure of Example 1 was repeated, except that the nitrogenatmosphere of the lower chamber was not substituted by dry air, tothereby conduct growth of a GaN crystal for 40 hours. In a mannersimilar to that of Example 1, the relationship between the growth timeand the oxygen concentration of the furnace internal atmosphere wasinvestigated. As shown in FIG. 3 , the oxygen concentration of thefurnace internal atmosphere was about 0.01 ppm, and almost constant.FIG. 5A is a photograph of a surface of the seed substrate (GaN crystalgrowth side), and FIG. 5B is a fluorescent image of the surface of theseed substrate. Through observation of the GaN crystal formed on theseed substrate, the average film thickness was found to be 0.5 mm.However, as shown in FIGS. 5A-5B, anomalous growth was observed at theperiphery of the seed substrate, such that no substantial growth of GaNwas observed at the periphery of the seed substrate. When the seedsubstrate was observed from the backside thereof, the GaN layer of theseed substrate at the anomalous growth region was found to be meltedback.

Comparative Example 2

The procedure of Example 1 was repeated, except that the atmosphere gasof the lower chamber was substituted by dry air immediately afterplacement of a crucible in a furnace in which a seed substrate and rawmaterials were placed, to thereby control the oxygen concentration ofthe atmosphere to >0.1 ppm. In this state, growth of a GaN crystal wasconducted for 64 hours. FIG. 6A is a photograph of a surface of the seedsubstrate (GaN crystal growth side), and FIG. 6B is a fluorescent imageof the surface of the seed substrate. The obtained GaN crystal was foundto have an average film thickness of 0.7 mm. However, as shown in FIGS.6A-6B, anomalous growth was observed at the periphery of the seedsubstrate, such that no substantial growth of GaN was observed at theperiphery of the seed substrate. When the seed substrate was observedfrom the backside thereof, the GaN layer of the seed substrate at theanomalous growth region was found to be melted back.

Second embodiment 1. Stack Structure of Semiconductor

FIG. 7 shows a stack structure CR of a semiconductor grown on a seedsubstrate through the flux method according to the embodiment. As shownin FIG. 7 , the seed substrate serves as a template substrate and has aGaN layer 13 grown through MOCVD on a buffer layer 12 formed on thesapphire substrate 11. Through employment of the GaN layer 13 as a seedcrystal, a GaN single crystal CR1 is grown through the flux method. TheGaN single crystal CR1 can be isolated by removing the sapphiresubstrate 11 from the stack structure CR, to thereby provide a GaNsubstrate. On the stack structure CR or the isolated GaN substrate, athick layer of a Group III nitride semiconductor such as GaN may begrown through hydride chemical vapor deposition, to thereby provide athick-film substrate.

2. Semiconductor Crystal Production Apparatus

FIG. 8 is a conceptual and general representation of a semiconductorproduction apparatus according to the embodiment. As shown in FIG. 8 , aproduction apparatus A1 has a crystal growth apparatus 1000, an Nacirculation apparatus 2000, a glovebox 3000, a joint chamber RM1, andpass boxes PB1 and PB2. The crystal growth apparatus 1000, shown in FIG.1 , is employed for growth of a Group III nitride semiconductor on aseed substrate. The Na circulation apparatus 2000 regulates the purityof Na material. The glovebox 3000 is provided for conducting anoperation of charging an Na material and a Ga material into thecrucible. The glovebox 3000 is provided with an oxygen meter forcontrolling the internal oxygen concentration, and a dew point meter forcontrolling the internal water content. The joint chamber RM1 isprovided for joining the crucible to the crystal growth apparatus 1000.The pass box PB1 is an apparatus for transferring a material, thecrucible, etc. to the glovebox 3000, while the pass box PB2 is anapparatus for transferring the crucible from the glovebox 3000 to thejoint chamber RM1.

3. Crystal Growth Apparatus

The crystal growth apparatus shown in FIG. 1 was employed. Theconfiguration of the apparatus is the same as described in relation tothe first embodiment, and detailed descriptions will be omitted.

4. Na Circulation Apparatus 4-1. Configuration of Na CirculationApparatus

FIG. 9 is a schematic configuration of the Na circulation apparatus 2000for employment in the semiconductor single crystal production methodaccording the embodiment. The Na circulation apparatus 2000 circulatesNa, to thereby enhance the purity of circulated Na. Since the Nacirculation apparatus 2000 is connected to the glovebox 3000, the Namaterial which has been highly purified by means of the Na circulationapparatus 2000 can be transferred into the glovebox 3000, in which thedew point and the atmosphere are controlled. Thus, the Na material fedinto the container disposed in the glovebox 3000 is prevented fromreacting with oxygen and water. The Na circulation apparatus 2000 has asupply tank 2100, a dump tank 2200, a cold trap 2300, an electromagneticpump 2400, an expansion tank 2500, a measuring tank 2600, an Nacollection outlet 2700, and pipes 2810, 2820, and 2830. The Nacirculation apparatus 2000 further includes other pipes, valves, and aheating apparatus for heating a relevant member. The heating apparatuscan maintain a temperature predetermined for the target member.

The Na circulation apparatus 2000 has a circulation path LP1 throughwhich the Na material in liquid form is passed. The circulation path LP1includes the cold trap 2300, the expansion tank 2500, theelectromagnetic pump 2400, and the pipes 2810, 2820, and 2830. Thesupply tank 2100 is a tank for feeding initial Na material to the Nacirculation apparatus 2000. Although the initial Na material hasconsiderably high purity, it contains a small amount of impurities. Theinitial Na material is solid. Since the supply tank 2100 is heated, theNa material becomes liquid. The liquid-form Na material is transferredto the dump tank 2200. The dump tank 2200 can absorb reflected shockwave.

The cold trap 2300 removes impurities contained in the Na material andalso functions as an Na purity controlling section for removing oxygenfrom or adding oxygen to Na. The cold trap 2300 will be furtherdescribed later. The electromagnetic pump 2400 returns the Na materialfrom the expansion tank 2500 to the cold trap 2300. The Na circulationapparatus 2000 causes the Na material to be circulated between the coldtrap 2300 and the expansion tank 2500, to thereby purify the Namaterial. The expansion tank 2500 is a tank for temporarily storingtherein the Na material from which impurities have been removed by meansof the cold trap 2300 (i.e., Na material storing section). The measuringtank 2600 measures the amount of Na material collected through the Nacollection outlet 2700. The Na material maintained in the measuring tank2600 has satisfactorily high purity. The Na collection outlet 2700serves as an outlet for feeding the purified Na material to the glovebox3000.

4-2. Operation Mechanism of Na Circulation Apparatus

As described above, the solid-form Na material is fed to the supply tank2100 of the Na circulation apparatus 2000. The Na material is heated bymeans of the supply tank 2100, to thereby form the correspondingliquid-form Na material. The liquid-form Na material is little by littletransferred to the dump tank 2200. Then, the liquid-form Na material inthe dump tank 2200 is transferred to the circulation path LP1. As aresult, the liquid-form Na material is circulated in the circulationpath LP1. The higher the temperature of the Na material, the higher thesolubility of oxygen in Na. The temperature of the cold trap 2300 is thelowest in the circulation path LP1. Thus, an impurity such as Na₂O isdeposited in the cold trap 2300. Na₂O is removed through a filter or thelike. During circulation in the circulation path LP1, the liquid-form Namaterial passes alternately and repeatedly through two different phases;i.e., a high temperature phase and a low temperature phase. Thus, oxygenis repeatedly removed from the liquid-form Na material, and ahigh-purity Na material can be recovered. The Na material fed throughthe Na collection outlet 2700 is a liquid. The liquid-form Na materialis poured into a container in the glovebox 3000 and cooled in thecontainer, to thereby form the corresponding solid.

4-3. Temperature of Cold Trap

The temperature (i.e., second temperature) of the cold trap 2300 isadjusted to 120° C. to 300° C. The temperatures (i.e., firsttemperatures) of the expansion tank 2500 and the pipes 2810, 2820, and2830 therearound are adjusted to >300° C. to ≤500° C., which is higherthan the temperature of the cold trap 2300. Since the temperature of thecold trap 2300 is lower than that of another section, impurities in theNa material can be removed by means of the cold trap 2300. There is acorrelation between the temperature set for the cold trap 2300 and theoxygen concentration of the Na material. Therefore, through selectingthe temperature (i.e., second temperature) of the cold trap 2300 to fallwithin a range of 120° C. to 300° C., the oxygen concentration or thelike of the Na material can be regulated.

5. Glovebox

FIG. 10 is a sketch of the glovebox 3000 employed in the productionmethod according to the embodiment. The glovebox 3000 is a chamber inwhich the Na material and other materials are treated. In order toprevent intrusion of air around the glovebox 3000 into the inside of theglovebox 3000, the internal pressure of the glovebox 3000 is set to apressure slightly higher than 1 atm. The glovebox 3000 has a housing3100, gloves GL1, windows WD1, a dew point meter 3110, an Ar circulationapparatus 3200, an Ar feed pipe 3310, an Ar exhaust pipe 3320, an Arventilation hole 3321, and an O₂ sensor (not illustrated). The housing3100 can maintain the internal atmosphere under predeterminedconditions. An operator conducts operations (e.g., treatment of Namaterial) in the glovebox 3000 by use of gloves GL1. The operatorvisually confirms the state inside the glovebox 3000 through the windowsWD1. The dew point of the glovebox 3000 is measured by means of the dewpoint meter 3110.

The Ar circulation apparatus 3200 is an apparatus for feeding andcollecting Ar gas. The Ar feed pipe 3310 is disposed for feeding Ar gasfrom the Ar circulation apparatus 3200 into the glovebox 3000. The Arexhaust pipe 3320 is disposed for collecting Ar gas into the Arcirculation apparatus 3200. The Ar exhaust pipe 3320 is branched to theAr ventilation hole 3321 in the pipe line thereof. On the downstreamside of the Ar ventilation hole 3321, the O₂ sensor is disposed. Byvirtue of the presence of the Ar circulation apparatus 3200, theinternal atmosphere of the glovebox 3000 is Ar. The internal oxygenconcentration of the glovebox 3000 is 0.05 ppm or less, which isdetermined by means of the O₂ sensor in the Ar ventilation hole 3321. Anexample of the O₂ sensor is DF-150E (product of Servomex). The internalwater content of the glovebox 3000 is 0.05 ppm or less. A value of 0.05ppm corresponds to a dew point of −94° C. The water content is measuredby means of the dew point meter 3110. An example thereof is anelectrostatic capacitance-based dew point meter MMS35 (product of GESensing & Inspection Technologies).

6. Impurity Concentration (Oxygen Intake Amount)

In this embodiment, a semiconductor single crystal is grown by theproduction apparatus A1, while the amount of impurities possiblymigrating into the crucible CB1 is controlled. The impurities mainlyinclude oxygen and water. In the crystal growth apparatus 1000, theoxygen concentration and the hydrogen concentration are controlled to ahigh degree.

7. Grains 7-1. Relationship Between Oxygen Intake Amount and Grains

There will next be described the amount of oxygen incorporated into themolten liquid and the grains formed on the seed substrate. FIGS. 11 and12 are sketches for describing the seed substrate and the grains grownthereon. As shown in the figures, grains Gr1 are grown on a seedsubstrate 10, and then a semiconductor layer Ep1 is grown. Each grainGr1 assumes just or nearly a shape of truncated hexagonal pyramid. Thegrains Gr1 of FIG. 11 are greater in size than grains Gr2 of FIG. 12 .As shown in FIG. 11 , when the amount of oxygen incorporated into themolten liquid is small, the grain size is larger. In contrast, as shownin FIG. 12 , when the amount of oxygen incorporated into the moltenliquid is large, the grain size is smaller. In addition, the larger thegain size, the smaller the stress of the semiconductor crystal grown inthe seed substrate. The possible reason for this is that the areas ofthe joined surface at which semiconductor crystals grown from unitgrains intermingle with one another decrease. The greater the grainsize, the smaller the warpage of the grown semiconductor single crystal.

7-2. Grain Size

As shown in FIG. 13 , the mean width W1 between the grains Gr1 at theinterface Sf1 between the seed substrate 10 and the grown semiconductorlayer Ep1 is preferably 10 μm to 100 μm. In order to more suitablyobserve the features, the observation cross-section is created byremoving the surface of the as-formed surface in a certain amount (somemicrometers to some ten micrometers) through polishing or a similartechnique, to thereby attain a flat surface. Then, the cross-section isobserved under a fluorescent microscope or a cathode luminescent device.As described hereinafter, through removal of oxygen atoms from the Namaterial, the grain size can increase, to thereby grow a semiconductorcrystal having small internal stress. Needless to say, this is essentialfor preventing contamination with oxygen in a semiconductor productiondevice and during the course of the production process.

8. Semiconductor Single Crystal Production Method

A first production method includes a maintenance step of maintaining theNa material in a storage chamber, and a semiconductor growth step ofadding an Na material, a Ga material, and a seed substrate into acrucible, to thereby realize the growth of a Group III nitridesemiconductor on the seed substrate. A second production method includesan Na purity controlling step of controlling the Na purity of the Namaterial by means of the Na circulation apparatus, and a semiconductorgrowth step of adding an Na material, a Ga material, and a seedsubstrate into a crucible, to thereby realize the growth of a Group IIInitride semiconductor on the seed substrate.

8-1. Seed Substrate Preparation Step

First, a seed substrate is provided. FIG. 14 is a schematic view of theseed substrate 10. As shown in FIG. 14 , the seed substrate 10 has thesapphire substrate 11, the buffer layer 12, and the GaN layer 13. Thebuffer layer 12 is formed on the c-plane of the sapphire substrate 11through MOCVD. The buffer layer 12 is formed of, for example, GaN, butmay be formed of TiN or AlN. Subsequently, the GaN layer 13 is formed onthe buffer layer 12, to thereby yield the seed substrate 10. The bufferlayer 12 and the GaN layer 13 serve as seed layers. Notably, in place ofGaN, the semiconductor formed on the sapphire substrate 11 through vaporphase growth may also be AlGaN, InGaN, or AlInGaN. The GaN layer 13undergoes melting back in the flux under certain conditions. In such acase, a part of the GaN layer 13 is dissolved in the flux. The seedsubstrate 10 may be commercially available. Alternatively, examples ofthe seed substrate 10 which may be used in the invention include amask-formed GaN substrate, a GaN substrate obtained by processing GaN,and a patterned GaN substrate obtained by selectively removing GaN.

8-2. Na Purity Control Step

First, the Na material is purified by means of the Na circulationapparatus 2000. Through heating a solid Na material, a correspondingliquid-form Na material is formed. In the liquid Na material, oxygen isdissolved in a larger amount as the temperature of the Na materialincreases. The temperature of the cold trap 2300 is 120° C. to 300° C.Since the temperature of the expansion tank 2500 is higher than that ofthe cold trap 2300, Na₂O or the like is deposited in the cold trap 2300.The thus-deposited impurities such as Na₂O are removed through a filteror the like. During passage of the molten Na material a plurality oftimes through the cold trap 2300 and the expansion tank 2500, impuritiessuch as Na₂O are gradually removed.

Thereafter, while the liquid Na material is weighed, the material ispoured from the Na circulation apparatus 2000 to the container placed inthe glovebox 3000. The molten Na material placed in the container in theglovebox 3000 is cooled in the glovebox 3000, to thereby form a solidthereof. The glovebox 3000 also serves as a maintenance chamber in whichthe dew point and oxygen concentration are regulated. The internalatmosphere of the glovebox 3000 contains ≤0.05 ppm oxygen and ≤0.05 ppmwater.

Then, in the glovebox 3000 the solid Na material is cut to pieces havingspecific dimensions. For example, a piece of a rectangular parallel-pipeform is cut from the Na material. The solid Na material obtained bycooling the liquid Na material from the Na circulation apparatus 2000may be used without cutting. Alternatively, a commercial Na material asis may be used without employing the Na circulation apparatus 2000. Inthe case where the surface of the Na material has been oxidized orattached with an oil for safely storing Na, the surface oxide layer oroil attached surface is removed by cutting.

8-3. Maintenance Step

The pieces of Na material are maintained in the glovebox 3000 for aspecific period of time. Specifically, as shown in FIG. 15 , pieces ofthe Na material are placed on a jig JIG1 disposed in the glovebox 3000.Through employment of the jig JIG1, the surface of the Na material canserve as a uniform reaction surface. When the jig JIG1 is provided withelectrical conductivity, electrostatic charging of Na can be prevented.In contrast, Ga is not necessarily maintained in the glovebox 3000, andmay be provided immediately before entrance to the crucible CB1. Thus,reaction of Ga with oxygen or water can be suppressed.

As shown in FIG. 16 , when an Na material Na1 is allowed to stand in theglovebox 3000, an Na material Na2 having a surface modified viaoxidation or hydroxidation is formed. The Na material Na2 consists of acore portion Na2a and a surface portion Na2b. The surface portion Na2bis a surface modification layer which has been formed through reactionof Na with oxygen or water present in the glovebox 3000. The coreportion Na2a is resistant to oxidation and other effects and maintainsthe same composition as that of the high-purity Na material Na1. Apurity of the high-purity Na material Na1 may be higher than 8 nines(99.999999% 8N). TABLE 1 shows conditions in the glovebox 3000,including oxygen concentration and water content. The internalatmosphere of the glovebox 3000 has an oxygen concentration of 0.05 ppmor less and greater than 0 ppm and may have an oxygen concentration of0.01 ppm or less and greater than 0 ppm. The internal atmosphere of theglovebox 3000 has a water content of 0.05 ppm or less and may have awater content of 0.01 ppm or less.

In the glovebox 3000, the Na material reacts mainly with oxygen orwater, to thereby form Na oxide or Na hydroxide on the surface thereof.In other words, the Na surface is modified, to thereby form amodification layer. The weight of the Na material increases by themodification reaction. Here, the Na surface modification weight ratio isdefined as follows. The weight of Na when the surface thereof has nosurface-modified portion is defined as a reference weight. Generally,the reference weight of Na refers to the weight of an Na piece which isobtained by cutting a highly purified Na material and weighing the pieceimmediately after cutting. The ratio of the weight of surface-modifiedNa to the weight of the reference weight is defined as a surfacemodification weight ratio. Thus, surface modification weight ratio isrepresented by (reference weight+weight increase by surfacemodification)/reference weight). Until the surface modification weightratio reaches a specific value falling within the range of 1.000002 to1.001, the Na material is maintained in the aforementioned atmosphere.The weight of the Na material is measured in the glovebox 3000 by meansof an electronic balance or a similar device. The Na material is placedon the electronic balance or the like. When the weight becomes aspecific constant value, the maintenance is stopped. An example of theelectronic balance is CPA225D (product of Sartorius). When the increasein weight of the Na material is regulated in, for example, the glovebox3000 in which oxygen concentration and water content are accuratelycontrolled, the surface modification weight ratio of Na can becontrolled with high reproducibility. Meanwhile, as the period of timefor allowing the Na material to stand in the glovebox 3000 becomeslonger, the weight of the Na material increases further. That is, thesurface modification weight ratio increases. The maintenance time(retention time) is, for example, 1 hour to 72 hours. Needless to say,the maintenance time may be set to another value. However, when oxygenand water contained in the glovebox 3000 are completely consumed,oxidation reaction is terminated. Thus, the maximum weight increase ofthe Na material and the maximum value of the surface modification weightratio are determined from the volume of the glovebox 3000 and theamounts of oxygen and water. Other than the cases of the maximum values,if the oxygen concentration and water content in the glovebox 3000 areaccurately regulated, the surface modification weight ratio of Na can becontrolled by the maintenance time.

TABLE 1 Oxygen concentration ≤0.05 ppm Water content ≤0.05 ppm Surfacemodification weight ratio of Na 1.000002 to 1.001 material

8-4. Semiconductor Growth Step

A semiconductor single crystal layer is grown on the seed substrate 10through a flux method. TABLE 2 shows the exemplary raw materials used inthe growth. The carbon ratio may be modified to fall within the range of0.1 mol % to 2.0 mol %. Notably, the values given in TABLE 2 are merelyexamples, and other values may be acceptable. Also, a doping element maybe further added. The semiconductor single crystal to be grown is asingle crystal of a Group III nitride semiconductor such as GaN. Inorder to reduce the oxygen concentration and water content to as low alevel as possible, the inside of the crystal growth apparatus 1000 isbaked prior to the growth. Through the preliminary baking, variation inoxygen concentration and water content in the furnace among growthbatches can be minimized.

Ga and Na are placed in the crucible CB1, and the seed substrate 10 isplaced on Na and Ga, while the crystal growth plane of the substrate isoriented upward. During transfer of the crucible CB1 from the glovebox3000 to the reaction chamber 1300, the crucible CB1 is placed in atriple-wall growth vessel, for the purpose of preventing reaction of theNa material with oxygen or water. In order to more effectively suppressthe reaction of the Na material, the path of the transfer is preferablyprovided in a nitrogen atmosphere. Subsequently, the crucible CB1 isplaced on the turn table 1330 in the reaction chamber 1300, and thepressure vessel 1100 is evacuated. The vessel is heated and pressurized,and the crucible CB1 is rotated, whereby a semiconductor single crystalis grown. In the semiconductor growth step, the seed substrate 10 fallsin a molten liquid of Na and Ga, and the semiconductor single crystal isgrown from the crystal growth plane of the seed substrate 10. The methodand timing of stirring may be arbitrarily chosen, and the growth may beperformed under no stirring. Also, the speed, rotational direction, andtiming of start/stop may be freely modified in the course of growth.

TABLE 2 Raw material Amount Ga/Na ratio 10 to 40 mol % C 0.1 mol % to2.0 mol % (to Na)

TABLE 3 shows conditions of the crucible used in the semiconductorsingle crystal formation step. The temperature and pressure of thesemiconductor single crystal growth are, for example, 870° C. and 3 MPa.The growth time is about 20 hours to 200 hours. Notably, the oxygenconcentration and water content of the internal atmosphere of thecrystal growth apparatus 1000 are determined by means of Qmass.

TABLE 3 Temperature about 700° C. to about 900° C. Pressure 2 MPa to 10MPa Stirring speed 0 rpm to 100 rpm Growth time 20 to 200 hours

9. Variations 9-1. Maintenance Step

In the maintenance step of a variation, the Na surface modificationweight ratio is regulated by feeding a gas mixture containing oxygen andwater into the glovebox 3000. Through this technique, the Na materialcan be reacted with oxygen or water within a short period of time. Inone specific procedure, the glovebox 3000 is evacuated, and then the Namaterial is placed in the glovebox 3000. A gas containing oxygen andwater is fed into the glovebox 3000. After oxygen and water contained inthe internal atmosphere of the glovebox 3000 have been completelyconsumed, reaction of the Na material with oxygen and water isterminated. Through the above procedure, the maximum weight increase ofthe Na material; i.e., the surface modification weight ratio, may becontrolled.

9-2. Controlling of Na Surface Modification Weight Ratio by MaintenanceChamber

The Na surface modification weight ratio may also be controlled by amaintenance chamber other than the glovebox 3000. The maintenancechamber allows control of the dew point and oxygen concentration. Themaintenance chamber may be evacuated, or various gases may be introducedthereinto. In one procedure, the Na material is placed in themaintenance chamber, and the chamber is evacuated. Then, a gascontaining oxygen and water is fed into the maintenance chamber, and thechamber is tightly closed. After oxygen and water contained in theinternal atmosphere of the maintenance chamber have been completelyconsumed, reaction of the Na material with oxygen and water isterminated. Through the above procedure, the maximum weight increase ofthe Na material; i.e., the maximum value of the surface modificationweight ratio, may be controlled.

9-3. Modification of Na in Semiconductor Growth Step

In the semiconductor growth step, a gas mixture containing oxygen andwater may be fed into the crystal growth apparatus 1000 accommodatingthe crucible CB1. Through this technique, the Na material can be reactedwith oxygen or water also in the semiconductor growth step. In onespecific procedure, a gas mixture containing oxygen and water may be fedthrough the gas intake inlet 1510.

9-4. Na Material Cutting Step and Semiconductor Growth Step

Preferably, after completion of the maintenance step; that is, aftercompletion of appropriate surface modification of Na, an Na materialcutting step is carried out. When the Na material is thicknesswisedivided into two almost equal portions, each cut surface has no surfacemodification layer (e.g., oxide film). As shown in FIG. 17 , a carbonmaterial is placed such that it is sandwiched by Na cut surfaces of thehigh-purity Na material. In other words, the carbon material is not incontact with an oxide or hydroxide plane of the Na material. In thesemiconductor growth step, when the Na material is melted, the carbonmaterial is dispersed with the Na material. Since the melting points ofsodium oxide and sodium hydroxide are higher than the melting point ofsodium, when the Na material has a sodium oxide plane or a sodiumhydroxide plane, dispersion of the carbon material is impeded. Forexample, as shown in FIG. 18 , when the oxide plane or hydroxide planeof the Na material is in contact with the carbon material, difficulty isencountered in dispersing the carbon material in Na. As shown in FIG. 17, when the carbon material is not in contact with the oxide or hydroxideplane of the Na material, the carbon material can be suitably dispersed.Also, variation in dispersion state of carbon can be minimized amonggrowth batches.

Example 2 1. Method of Experiment

A GaN single crystal semiconductor was produced by means of theproduction apparatus A1. The seed substrate was produced by forming aGaN layer on a sapphire substrate. In Example 2, the period of time forallowing the Na material to stand (i.e., surface modification time) wasvaried, whereby the surface modification weight ratio of the Na materialwas tuned.

2. Results of Experiment

FIG. 19 is a graph showing the relationship between Na surfacemodification weight ratio and warpage or amount of miscellaneouscrystals. In FIG. 19 , the horizontal axis represents the Na surfacemodification weight ratio, and the vertical axis represents the extentof warpage (reciprocal radius of curvature (1/m)) and the weight ofgenerated miscellaneous crystals (g).

As shown in FIG. 19 , the greater the Na surface modification weightratio, the greater the curvature of the substrate. Also, the greater theNa surface modification weight ratio, the smaller the weight ofgenerated miscellaneous crystals. That is, from the viewpoint ofpreventing warpage, the surface modification weight ratio of the Namaterial is preferably small. From the viewpoint of suppressing theamount of generated miscellaneous crystals, the surface modificationweight ratio of the Na material is preferably large. The extent ofwarpage and the amount of generated miscellaneous crystals are in atrade-off relation.

As shown in FIG. 19 , when the surface modification weight ratio of theNa material is 1.000002 to 1.001 (range R1 in FIG. 19 ), the warpage ofthe grown semiconductor is about 0.5/m or less, and the amount ofgenerated miscellaneous crystals is about 15 g or smaller. Thus, atleast one of the warpage of the semiconductor and the amount ofgenerated miscellaneous crystals is suppressed. Also, the surfacemodification weight ratio of the Na material may be 1.000002 to 1.0001.When the surface modification weight ratio of the Na material is1.000002 to 1.00005 (range R2 in FIG. 19 ), the warpage of the grownsemiconductor is about 0.4/m or less. Thus, the warpage of thesemiconductor is suppressed. When the surface modification weight ratioof the Na material is 1.00002 to 1.001 (range R3 in FIG. 19 ), theamount of generated miscellaneous crystals is about 5 g or smaller.Thus, the amount of generated miscellaneous crystals is suppressed. Arange of the surface modification weight ratio of the Na material from1.00002 to 1.0001 is preferred for reducing the amount of generatedmiscellaneous crystals. When the surface modification weight ratio ofthe Na material is 1.00002 to 1.00005 (range R4 in FIG. 19 ), thewarpage of the grown semiconductor is about 0.4/m or less, and theamount of generated miscellaneous crystals is about 5 g or smaller.Thus, the warpage of the semiconductor layer and the amount of generatedmiscellaneous crystals are suppressed.

TABLE 4 shows the results of FIG. 19 .

TABLE 4 Na surface modification Warpage Miscellaneous crystals weightratio (1/m) (g) 1.000004 0.112 14.795 1.000038 0.333 3.284 1.0000900.500 0

As the warpage of a semiconductor decreases, the dislocation density ofthe semiconductor tends to decrease, and the crystallinity thereof tendsto increase. In addition, as the warpage decreases, the semiconductorstructure can be easily flattened by processing, to thereby narrow theoff angle distribution. However, when the resultant semiconductor hasconsiderable warpage, the thus-grown semiconductor single crystal iseasily separated from the seed substrate. When the amount of generatedmiscellaneous crystals is large, the crystallinity of the Group IIInitride semiconductor is impaired, to thereby reduce the productionyield. Therefore, generally, a smaller amount of generated miscellaneouscrystals is preferred. However, in order to ensure the quality of thetarget semiconductor products, in some cases, those skilled in the artmay intentionally select the conditions where miscellaneous crystals maygenerate.

Third Embodiment

Virtually the same production apparatus as employed in the secondembodiment is used, and only the features different from those of thesecond embodiment will be described. In the third embodiment, themaintenance step in the glovebox is not carried out in the Na puritycontrol step of the second embodiment. The third embodiment ischaracterized by enhancing the purity of Na by means of the Nacirculation apparatus described in relation to the second embodiment.The thus-purity-controlled molten Na is directly fed to the crucible.The purity of Na is controlled by means of the temperature of the coldtrap 2300 (i.e., second temperature). As the temperature of the coldtrap 2300 is lower, the purity of Na increases, and the oxygen contentdecreases.

As shown in FIG. 10 , a material such as Ga is placed in the crucibleCB1 disposed in the glovebox 3000. Then, the high-purity molten Na whosepurity has been highly enhanced by means of the Na circulation apparatus2000 is poured into the crucible CB1, with the feed amount beingmonitored. As a result, Ga is immersed in the molten Na. Subsequently,the seed substrate 10 is placed on the molten Na, while the crystalgrowth plane of the substrate is oriented upward. In this case, themolten Na is in contact with the bottom and wall of the crucible CB1,and the crucible is closed with the seed substrate 10. As a result, thearea of the molten Na which is in contact with the environmentalatmosphere is minimized, whereby oxidation of the molten Na in thecrucible is prevented.

Example 3 1. Method of Experiment

The same seed substrate as employed in Example 2 was used. That is, thesubstrate was a template substrate formed of a sapphire substrate onwhich a GaN layer had been formed. The relationship between thetemperature of the cold trap 2300, and the extent of warpage of thesubstrate after growth of GaN through the flux method or the amount ofgenerated miscellaneous crystals was determined. The temperature of thecold trap 2300 was varied from 100° C. to 300° C. The temperature of theexpansion tank 2500 was fixed at 400° C.

2. Results of Experiment

FIG. 20 is a graph showing the relationship between the temperature ofthe cold trap 2300, and the warpage of the substrate or the amount ofgenerated miscellaneous crystals. In FIG. 20 , the horizontal axisrepresents the temperature of cold trap, and the vertical axisrepresents the curvature of the substrate (i.e., the extent of warpageof the substrate) (1/radius of curvature (m)) and the weight ofgenerated miscellaneous crystals (g). As shown in FIG. 20 , the higherthe temperature of the cold trap 2300, the greater the warpage of thesubstrate. Also, the higher the temperature of the cold trap 2300, thesmaller the weight of generated miscellaneous crystals. That is, thehigher the temperature of the cold trap 2300, the smaller the amount ofremoved impurities. In this case, the purity of Na decreases, and theoxygen content increases. From the viewpoint of preventing warpage, thetemperature of the cold trap 2300 is preferably lower. From theviewpoint of reducing the amount of generated miscellaneous crystals,the temperature of the cold trap 2300 is preferably higher. In otherwords, from the viewpoint of preventing warpage, the purity of Na ispreferably higher (i.e., lower oxygen content), and, from the viewpointof suppressing generation of miscellaneous crystals, the purity of Na ispreferably lower (i.e., higher oxygen content). Thus, suppression ofwarpage and suppression of generation of miscellaneous crystals are in atrade-off relation.

When the temperature of the cold trap 2300 is 120° C. to 300° C. (rangeR1 in FIG. 20 ), at least one of the warpage of semiconductor and theamount of generated miscellaneous crystals is suppressed. In the rangeR1, the curvature is about 0.4/m or less, and the amount of generatedmiscellaneous crystals is about 8 g or smaller. When the temperature ofthe cold trap 2300 is 120° C. to 230° C. (range R2 in FIG. 20 ), thecurvature is about 0.3/m or less. Thus, the warpage of semiconductor issuppressed. When the temperature of the cold trap 2300 is 180° C. to300° C. (range R3 in FIG. 20 ), the amount of generated miscellaneouscrystals is about 2 g or smaller. Thus, the amount of generatedmiscellaneous crystals is suppressed. When the temperature of the coldtrap 2300 is 180° C. to 230° C. (range R4 in FIG. 20 ), the curvature is0.3/m or less, and the amount of generated miscellaneous crystals is 2 gor smaller. Thus, the warpage and the amount of generated miscellaneouscrystals are suppressed. The merits of suppression of the warpage of thesubstrate after growth of the GaN semiconductor and the generation ofmiscellaneous crystals are described in relation to the secondembodiment.

In the Na purity control step, the temperature of the cold trap 2300 maybe adjusted to 300° C. or thereabouts. In this case, oxygen present inthe environment around the Na circulation apparatus 2000 readily entersthe cold trap 2300, and the intake oxygen migrates into the molten Na.As a result, the oxygen concentration of Na increases. As describedabove, in the Na purity control step, the oxygen concentration of Na foruse in the growth can be appropriately regulated by controlling thetemperature of the cold trap 2300.

Features Generally Applicable to All Embodiments 1. Use of Multi-PointSeed (MPS) Substrate

FIGS. 21A and 21B are a cross-section and a plan view of an MPSsubstrate. On the sapphire substrate 11, a patterned SiO₂ dielectricmask is formed. Patterning is performed through photolithography. On themask, a buffer layer 12 and a GaN single crystal layer are sequentiallygrown. A GaN single crystal is grown on a part not covered with themask. After that, the mask is removed. As shown in FIG. 21A, posts 13Ahaving a hexagonal pyramid shape are formed. FIG. 21B is a top view ofthese posts which are arranged into a triangular grid. The arrangementcorresponds to a honeycomb structure.

In the aforementioned first to third embodiments, the above-mentionedMPS substrate may be used, and GaN may be grown on the substrate throughthe flux method. A mechanism for moving up and down the seed substrateis provided in the furnace. In a specific case, an MPS substrate isfirstly immersed in molten Na-Ga, and GaN is grown around the posts 13A.More specifically, GaN is grown on each hexagonal pyramid having a(10-11) plane (i.e., S-plane) as a facet plane. The step is a firstgrowth step. In the first growth step, the growth spontaneously stops ina specific stage without filling the space between posts 13A with GaN.Subsequently, the MPS substrate was repeatedly subjected to manyrepetitions of up-and-down operations (i.e., immersion in and pullingfrom the molten Na-Ga), to thereby grow GaN in the space where no postis present. The facet plane was a (10-11) plane in the region near theunderlayer substrate 11 (i.e., a lower region), and a (10-12) plane inthe region far from the underlayer substrate 11 (i.e., an upper region)(r-plane). This step is a second growth step. The second growth step iscalled a “flux film coat (FFC).” When the second step is complete, thespace between posts was filled with grown GaN. After completion of thesecond growth step, the MPS substrate is immersed in molten Na-Ga for aspecific period of time, whereby GaN is grown along the c-axisdirection. This step is a third growth step. In the third growth step,the top surface is flattened and assumed the c-plane of GaN.

After the growth of a c-plane GaN layer having a specific thickness fromthe MPS substrate, the furnace is cooled. When the GaN-formed substrateis removed from the furnace, the grown GaN layer is readily peeled fromthe underlayer substrate 11. The peeling surface of the GaN layer ispolished. And also the growth surface of the GaN on which asemiconductor layer will be formed. The thus-polished GaN is used as asubstrate for providing a variety of devices. For example, a thick GaNlayer can be further formed thereon through HVPE for high-speed growth.Such a thick GaN layer may be used as a substrate for a device such as afield-effect transistor or a light-emitting device.

A MPS substrate having a shape as shown in FIG. 22A may be used. Each ofthe posts 13B may be formed in a hexagonal column or a hexagonalpyramid. These posts are arranged into a triangular grid as shown in theplan view of FIG. 21B. The arrangement corresponds to a honeycombstructure. In this case, GaN 14 was grown on flat top surfaces of theposts 13B for 40 hours as the first growth step (FIG. 22B).Subsequently, as the second growth step was performed for 80 hours. Inthis case, the space (groove) 15 between posts was filled by growing GaN16 (FFC) on a facet plane of the groove 15 at the junction of GaN 14grown in the first growth step (FIG. 22C). Then, as the third growthstep, GaN 17 was uniformly grown along the c-axis direction (FIG. 22D).

Example 4

An MPS substrate (diameter: 6 inches) was used. The preparation wasperformed in a glovebox under Ar in which the oxygen concentration andwater content were controlled to low levels. More specifically, theoxygen concentration was controlled to be lower than 0.05 ppm, and thewater content was adjusted such that the dew point of the internalatmosphere was lower than −90° C. In purification of Na, the cold trap2300 shown in FIG. 9 was adjusted to 180° C. When the purity reached atarget value through circulation of molten Na, the molten Na was removedfrom the system and solidified. A weighed aliquot thereof was placedinto a crucible. Then, Ga and carbon were added to the crucible. TheGa/Na ratio was 18 mol %, and the ratio of carbon to Na was 0.6 mol %.An MPS substrate or an MPS substrate held by a supporting member wasadded to the crucible containing the raw materials, and the crucible wastransferred into a growth furnace. The furnace was evacuated to 0.2 Pa,and then nitrogen was fed into the furnace so as to adjust the internalpressure to 3.0 MPa.

Subsequently, the furnace was heated to 870° C. (i.e., GaN growthtemperature), and the MPS substrate was immersed in molten Na-Ga at thetiming of 20 hours passing after the temperature reaching 870° C. TheFFC growth of GaN was performed at the timing of 40 hours passing afterthe MPS substrate was immersed in molten Na-Ga. The growth of GaNthrough a flux method is performed for 220 hours in total. Specifically,the first growth step was performed for 40 hours, the second growth stepfor 80 hours, and the third growth step for 60 hours. Through the firstto third steps, the growth temperature and pressure were constantly setto 870° C. and 3.0 MPa. According to the above growth technique, ac-plane GaN semiconductor having a diameter of 6 inches was yielded. Atthis time, generation of miscellaneous crystals and occurrence ofwarpage of the semiconductor can be suppressed by controlling the oxygenconcentration in the molten liquid of Na in the same way as in Examples1 to 3.

In Example 4, alternatively, highly purified molten Na may be directlyfed to a crucible in a manner similar to that of the third embodiment,and Ga, C, and MPS SUBSTRATE may be added thereto, to thereby conductcrystal growth.

2. Reuse as Seed Substrate

The Group III nitride semiconductor which has been produced in thesemiconductor growth may also be used as a seed substrate. In such acase, the semiconductor grown through the flux method is separated fromthe growth substrate, to thereby provide a new semiconductor substrate.The new substrate can be employed as a seed substrate for use in theflux method. On the semiconductor substrate, a thick Group III nitridesemiconductor may be grown through HVPE, to thereby prepare a thick filmsubstrate. By using a seed substrate having small off-angledistribution, dislocation density or warpage, a thick semiconductorsubstrate exhibiting better quality as compared to conventionalsubstrate can be provided.

3. Diversion to Device Substrate

Through forming device layers on the thus-produced semiconductorsubstrate through MOCVD, various devices such as an LED and afield-effect transistor can be fabricated. Alternatively, GaN is grownat high speed through HVPE on the GaN layer obtained through theaforementioned flux method, to thereby form a thick GaN layer, anddevice layers are grown through MOCVD on the thick GaN layer, to therebyproduce corresponding devices. In this case, the produced devices areattached to an underlayer substrate. Alternatively, the thick GaN layermay be sufficiently grown, and the underlayer substrate is removed,whereby a substrate-free device is produced.

What is claimed is:
 1. A method for producing a Group III nitridesemiconductor comprising feeding a nitrogen-containing gas into a moltenmixture of a Group III metal and a flux placed in a furnace, to therebygrow a Group III nitride semiconductor on a seed substrate, wherein theGroup III nitride semiconductor is grown on the seed substrate, whilecontrolling the surface modification weight ratio, which is defined asthe ratio of the weight of Na including a portion surface-modifiedthrough oxidation or hydroxidation to the weight of Na when the surfacethereof has no surface-modified portion as a reference weight, with Naserving as the flux.
 2. The Group III nitride semiconductor productionmethod according to claim 1, wherein the surface modification weightratio is 1.000002 to 1.001.
 3. The Group III nitride semiconductorproduction method according to claim 1, wherein the surface modificationweight ratio is 1.00002 to 1.0001.
 4. The Group III nitridesemiconductor production method according to claim 1, wherein thesurface modification weight ratio is 1.000002 to 1.00005.
 5. The GroupIII nitride semiconductor production method according to claim 1,wherein the surface modification weight ratio is modified by maintainingNa in a specific environment outside the furnace before its entrance tothe furnace.
 6. The Group III nitride semiconductor production methodaccording to claim 1, wherein the surface modification weight ratio ismodified by feeding a gas mixture containing at least one of oxygen andwater to the furnace.
 7. The Group III nitride semiconductor productionmethod according to claim 5, wherein at least one of the oxygenconcentration and the water content of the specific environment arecontrolled to ≤0.05 ppm and >0 ppm, respectively.
 8. The Group IIInitride semiconductor production method according to claim 5, wherein agas mixture containing at least one of oxygen and water may beintroduced to the specific environment.
 9. The Group III nitridesemiconductor production method according to claim 1, wherein an Napiece whose surface modification weight ratio has been controlled iscut, and a carbon material is placed on a surface of the cut piece whichhas undergone no oxidation or hydroxidation, followed by placing theresultant piece in the furnace.